Modifying porous sorbents for the purpose of improving their binding properties often results in
decreased surface area and inaccessible pores. We chose the polymers of intrinsic microporosity
(PIMs) as an excellent platform for developing a universal strategy for effective modification of
functional groups without sacrificing important properties. This is because of their inherent solubility
and the ensuing rigorous, molecular analysis. We reported the first noninvasive functionalization of
PIMs with amidoxime, resulting in an increase in carbon dioxide capacity by 17% and surface area by
20% without affecting its film-forming ability. The introduction of amidoxime was achieved through a
rapid reaction of nitrile groups of PIM-1 with hydroxyl amine under reflux conditions and confirmed
through common analytical techniques. Additionally, we have successfully transformed PIM-1 nitriles
into four new functional groups – ketones, alcohols, imines, and hydrazones – in a single step using a
non-solvent approach that preserves surface area. These modifications are simple, scalable, and
reproducible, and offer unique new directions for chemical modification of porous materials.